US007691792B1

(12) Ulllted States Patent (10) Patent N0.: US 7,691,792 B1 Fisher et a]. (45) Date of Patent: Apr. 6, 2010

(54) LUBRICANT COMPOSITIONS (56) References Cited

(75) Inventors: Karl Fisher, Petaluma, CA (U S); Frank U'S' PATENT DOCUMENTS X_ Woolard’ Greenbrae’ C A (Us) 3,794,692 A 2/ 1974 Komatsu et a1.

_ 3,859,374 A 1/1975 Komatsu et a1. (73) Assrgnee: Amyris Biotechnologies, Inc., 6,491,809 B1 12/2002 Briot et a1.

Emeryville, CA (US) 7,399,323 B2 7/2008 Renninger et a1. * _ _ _ _ _ 7,592,295 B1 9/2009 Fisher et a1.

( ) Notice: Subject to any disclaimer, the term of this 2005/0023188 A1 2/2005 Connor patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS

(21) APP1-NO-3 12/577,093 Zhang, et al., Kunchong Xuebao, (1988) 3 1(4), 435-8.

(22) Filed: Oct. 9, 2009 Primary ExamineriGlenn Caldarola - - Assistant Examinerilim Goloboy RltdU.S.A l t Dt

e a 6 PP lea Ion a a (74) Attorney, Agent, or Firmilones Day

(60) Provisional application No. 61/244,406, ?led on Sep. 21, 2009. (57) ABSTRACT

(51) Int. Cl. Compositions comprising a farnesane dimer and/or a fame C10M 169/04 (2006.01) sene dimer and a compound selected from squalene, squalene C07C 13/18 (2006.01) and dehydrosqualene are described. The compositions pro

(52) US. Cl. ....................................... .. 508/110; 585/23 Vided comprise Conventional additives. Methods of making (58) Field of Classi?cation Search ............... .. 508/110; and using the Compounds and Composition are also disclosed

585/23 See application ?le for complete search history. 20 Claims, 1 Drawing Sheet

US. Patent Apr. 6,2010 US 7,691,792 B1

40 35 /

30 _"'_ 0C

25 / -- 100°C cSt 20 /

15 10 5 MP

0 . I . F

0 20 40 6O 80 1 00 % Distilted Farnesane Dimer

F1G.1

1 40 1 20 1 00 80

VI 60 40 20

0 20 4O 60 80 100

‘7; Disti?ed Famesane Dimer

FIG.2

US 7,691,792 B1 1

LUBRICANT COMPOSITIONS

PRIOR RELATED APPLICATIONS

This application claims priority to Us. Provisional Patent Application No. 61/244,406, ?led Sep. 21, 2009, the contents of Which are incorporated herein by reference in their entire ties.

FIELD

Provided herein are compositions comprising a farnesane dimer and/ or a famesene dimer and a compound selected from squalane, squalene and dehydrosqualene. Also provided are methods of making and using the compositions. In certain embodiments, the compositions provided herein have use as lubricants and lubricity enhancers.

BACKGROUND

Considerable effort has been expended to develop lubri cant compositions for use in industrial applications associ ated With the automotive, tractor, airline, railroad, metal

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2 Working industry and the like. There is a continuing demand for cost-effective lubricant compositions exhibiting improved characteristics.

SUMMARY

In one embodiment, provided herein are compositions comprising farnesane dimer II-A and a compound selected from squalane, squalene, and (6E,llE,l8E)-2,6,l9,23-tet ramethyl-l0, l 5-dimethylenetetracosa-2,6,l 1,18,22-pen taene, Where II-A is

II-A

In one embodiment, the compositions further comprise farnesane dimer II-B, Where II-B is:

II-B

In another embodiment, the compositions further comprise a farnesane dimer selected from:

II-C

II-D

In another embodiment, the compositions further comprise a famesene dimer selected from:

US 7,691,792 B1

-continued

In one embodiment, a composition provided herein com prises famesane dimer II-A or farnesane dimer II-B, and a compound selected from squalane, squalene, and (6E,11E, 18E) -2,6, 1 9,23 -tetramethyl-10, 15 -dimethylenetetracosa-2, 6,1 1,18,22-pentaene. In one embodiment, a composition pro vided herein comprises farnesane dimer H-A or farnesane dimer II-B, and squalane. In another embodiment, a compo sition provided herein comprises I-A, I-B, I-C, I-D, II-A, II-B, II-C or H-D and a compound selected from squalane, squalene, and (6E,11E,18E)-2,6,19,23-tetramethyl-10,15 dimethylenetetracosa-2,6,1 1,18,22-pentaene. In one embodiment, a composition provided herein comprises far nesane dimer II-A and squalane.

In certain embodiments, compositions provided herein have a viscosity index of about 80 or greater according to ASTM D 2270. In certain embodiments, the viscosity index is from about 90 to about 150 according to ASTM D 2270.

In certain embodiments, the compositions provided herein can be used in a Wide variety of applications, including but not limited to, applications associated With the automotive, trac tor, airline, and railroad industries including engines, trans missions, and the like, metal-Working ?uids, quench ?uids, greases, crankcase lubricants, poWer transmission ?uids, vehicle axle applications, hydraulic systems, heavy duty gear oils, and rotating machinery such as stationary engines, pumps, gas turbines, compressors, Wind turbines, and the like. Stationary engines include fuel and gas poWered engines that are not associated With the automotive, tractor, airline, and railroad industries. Also provided are methods of making the compositions.

In certain embodiments, compositions provided herein are readily biodegradable. In certain embodiments, compositions provided herein are loW in toxicity and pose little or no harm to aquatic organisms or surrounding vegetation. These quali ties are particularly useful for applications in environmentally sensitive areas such as marine ecosystems, and for those With

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a high potential of being lost to the surrounding environment. In certain embodiments, compositions provided herein can be derived from readily available, reneWable materials.

In certain embodiments, provided herein is a method of lubricating a machine by operating the machine in contact With a composition provided herein. The compositions can be used for lubricating any machine that needs lubrication. Exemplary machines include, but are not limited to engines, pumps, gas turbines, compressors, Wind turbines, and the like. In certain embodiments, the engine is a fuel and/or gas poWered engine associated With the automotive, tractor, air line, and railroad industries. In certain embodiments, the engine is a stationary engine, including a fuel and/or gas poWered engine that is not associated With the automotive, tractor, airline, and railroad industries.

In certain embodiments, provided herein is a machine com prising a composition provided herein.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shoWs the relationship of kinetic viscosity for vari ous blends of squalane and farnesane dimer II-A at 40 and 1000 C.

FIG. 2 shoWs viscosity index for various blends of squalane and farnesane dimer II-A.

DEFINITIONS

In the folloWing description, all numbers disclosed herein are approximate values, regardless Whether the Word “about” or “approximate” is used in connection thereWith. Numbers may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical range With a loWer limit, RL, and an upper limit, RL, is disclosed, any number falling Within the range is speci?cally disclosed. In particular, the folloWing numbers Within the range are speci?cally dis closed: R:RL+k*(RUiRL), Wherein k is a variable ranging from 1 percent to 100 percent With a 1 percent increment, i.e.,

US 7,691,792 B1 5

k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . ,

50 percent, 51 percent, 52 percent, . . . , 95 percent, 96 percent,

97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range de?ned by tWo R numbers as de?ned in the above is also speci?cally disclosed.

As used herein, “[3-Farnesene” refers to a compound hav ing the following formula:

6 or a stereoisomer thereof. In some embodiments, the [3-far nesene comprises a substantially pure stereoisomer of [3-far nesene. In other embodiments, the [3-farnesene comprises a mixture of stereoisomers, such as cis-trans isomers. In further embodiments, the amount of each of the stereoisomers in the [3-famesene mixture is independently from about 0.1 Wt. % to about 99.9 Wt. %, from about 0.5 Wt. % to about 99.5 Wt. %, from about 1 Wt. % to about 99 Wt. %, from about 5 Wt. % to about 95 Wt. %, from about 10 Wt. % to about 90 Wt. %, from about 20 Wt. % to about 80 Wt. %, based on the total Weight of

the [3-famesene mixture. As used herein, “squalane” refers to a compound having

the folloWing formula:

As used herein, “squalene” refers to a compound having the folloWing formula:

35 As used herein, “dehydrosqualene” or “(6E,1 1E,18E)-2,6,

19,23 -tetramethyl-10,15 -dimethylenetetracosa-2,6,1 1,18, 22-pentaene” refers to a compound having the folloWing for mula:

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DESCRIPTION OF EMBODIMENTS

In one embodiment, provided herein are compositions comprising famesane dimer H-A and a compound selected from squalane, squalene, and (6E,11E,18E)-2,6,19,23-tet ramethyl-10,15-dimethylenetetracosa-2,6,1 1,18,22-pen taene, Where II-A is

II-A

In one embodiment, the compositions further comprise famesane dimer II-B, Where II-B is:

US 7,691,792 B1 7

H-B

10

In another embodiment, the compositions further comprise a famesane dimer selected from:

II-C

, and

H-D

In another embodiment, the compositions further comprise a famesene dimer selected from:

I-A

US 7,691,792 B1

In one embodiment, a composition provided herein com prises famesane dimer II-A or farnesane dimer II-B, and a compound selected from squalane, squalene, and (6E,11E, 18E) -2,6, 1 9,23 -tetramethy1-10, 15 -dimethy1enetetracosa-2, 6,11,18,22-pentaene.

In another embodiment, a composition provided herein comprises famesene dimer and/or farnesane dimer I-A, I-B, I-C, T-D, II-A, II-B, II-C or II-D, and a compound selected from squalane, squalene, and (6E,11E,18E)-2,6,19,23-tet ramethy1-10,15-dimethy1enetetracosa-2,6,1 1,18,22-pen taene.

In one embodiment, provided herein is a composition com prising famesane dimer II-A, and squalane. In one embodi ment, the composition further comprises farnesane dimer II-B. In one embodiment, the composition further comprises I-A, I-B, I-C, I-D, II-C, II-D or a mixture thereof.

In certain embodiments, the amount of famesane dimer II-B in compositions provided herein about 0.1% or greater based on the total Weight of the composition. In certain embodiments, the amount of famesane dimer II-A in compo sitions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the amount of farnesane dimer II-A in compositions provided herein is from about 1 to about 95% based on the total Weight of the composition. In certain embodiments, the amount of famesane dimer II-A in compositions provided herein is about 1, 3, 5, 7, 10, 12, 15, 17, 20, 23, 25, 27, 30, 33, 35, 37, 40, 43, 45, 47, 50, 60, 70, 80, 90, or 95% or greater based on the total Weight of the composition.

In certain embodiments, the amount of famesane dimer II-B in compositions provided herein about 0.1% or greater based on the total Weight of the composition. In certain embodiments, the amount of famesane dimer II-B in compo sitions provided herein about 1% or greater based on the total Weight of the composition. In certain embodiments, the amount of farnesane dimer II-A in compositions provided herein is from about 1 to about 80% based on the total Weight of the composition. In certain embodiments, the amount of famesane dimer H-A in compositions provided herein is about 1, 3, 5, 7, 10, 12, 15, 17, 20, 23, 25, 27, 30, 33, 35, 37, 40,43, 45, 47, 50, 60, 70, or 80% or greater based on the total Weight of the composition.

In certain embodiments, the total amount of famesene dimers and/or famesane dimers I-A, I-B, I-C, I-D, I-C and II-D in compositions provided herein is about 0.1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of famesene dimers and/or famesane dimers I-A, I-B, I-C, I-D, II-C and H-D in compo sitions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of famesene dimers and/or farnesane dimers I-A, I-B, I-C, I-D, II-C and II-D in compositions provided herein is about 1 to 20% or greater based on the total Weight of the farnesene dimers. In certain embodiments, the total amount of farnesene dimers and/or farnesane dimers I-A, I-B, I-C, I-D, II-C and II-D in compositions provided herein is about 0.1, 1, 2, 3, 4, 5, 6, 10, 12, 15, 17, 20, 25, 30, 35, 40 or 50% or greater based on the total Weight of the famesene dimers.

In certain embodiments, the total amount of squalane, squalene and dehydrosqualene in compositions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of squalane, squalene and dehydrosqualene in compositions provided herein is from about 5 to about 90% based or greater on the total Weight of the composition. In certain embodi ments, the total amount of squalane, squalene and dehy

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1 0 drosqualene in compositions provided herein is about 1, 3, 5, 7,10,12,15,17,20,23,25,27,30,33,35,37,40,43,45,47, 50, 60, 70, 80 or 90% or greater based on the total Weight of the composition.

In certain embodiments, the amount of squalane in com positions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of squalane in compositions provided herein is from about 1 to about 95% or 5 to about 90% or greater based on the total Weight of the composition. In certain embodi ments, the total amount of squalane in compositions provided herein is about 1, 3, 5,7, 10, 12, 15, 17, 20, 23, 25, 27, 30,33, 35, 37, 40, 43, 45,47, 50, 60,70, 80, or 90% or greater based on the total Weight of the composition.

In certain embodiments, the amount of squalene in com positions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of squalene in compositions provided herein is from about 1 to about 90%, about 1 to about 50%, about 1 to about 30% or greater based on the total Weight of the com position. In certain embodiments, the total amount of squalene in compositions provided herein is about 1,3, 5, 7, 10, 12, 15, 17, 20, 23, 25,27, 30, 33, 35, 37,40, 43, 45, 47, 50, 60, 70, 80 or 90% or greater based on the total Weight of the composition.

In certain embodiments, the amount of dehydro squalene in compositions provided herein is about 1% or greater based on the total Weight of the composition. In certain embodiments, the total amount of dehydrosqualene in compositions pro vided herein is from about 1 to about 90%, about 1 to about 50%, about 1 to about 30% or greater based on the total Weight of the composition. In certain embodiments, the total amount of dehydrosqualene in compositions provided herein is about 1, 3, 5, 7, 10, 12, 15, 17, 20, 23, 25, 27, 30, 33, 35, 37, 40, 43, 45, 47, 50, 60, 70, 80 or 90% or greater based on the total Weight of the composition.

In certain embodiments, the compositions provided herein have kinetic viscosity of about 3 centistokes (cSt) or greater at 1000 C. In certain embodiments, the compositions provided herein have kinetic viscosity of about 4 centistokes (cSt) or greater at 1000 C. In certain embodiments, the compositions provided herein have kinetic viscosity from about 3 cSt to about 10 cSt, from about 4 cSt to about 8 cSt, or from about 4 cSt to about 6 cSt at 1000 C. In certain embodiments, the compositions provided herein have kinetic viscosity from about 3 centistokes (cSt) to about 10 cSt, from about 4 cSt to about 8 cSt, or from about 4 cSt to about 6 cSt at 1000 C. In certain embodiments, the compositions provided herein have kinetic of about 4, 5, or 6 cSt at 1000 C.

In certain embodiments, the compositions provided herein have kinetic viscosity of about 15 cSt or greater at 400 C. In certain embodiments, the compositions provided herein have kinetic viscosity of about 20 cSt or greater at 400 C. In certain embodiments, the compositions provided herein have kinetic viscosity from about 15 cSt to about 40 cSt, from about 20 cSt to about 40 cSt, or from about 20 cSt to about 30 cSt at 400 C. In certain embodiments, the compositions have kinetic vis cosity of about 20, 25, 30 or 35 cSt at 400 C. The kinetic viscosity of the compositions disclosed herein can be mea sured according to ASTM D 445.

In certain embodiments, the compositions provided herein have dynamic viscosity of about 10 cP or greater at 400 C. In certain embodiments, the compositions provided herein have dynamic viscosity of about 15 cP or greater at 400 C. In certain embodiments, the compositions provided herein have dynamic viscosity from about 10 cP to about 40 cP, from about 15 cP to about 30 cP, or from about 15 cP to about 25 cP

US 7,691,792 B1 11

at 400 C. In certain embodiments, the compositions provided herein have dynamic viscosity of about 15, 17, 20, 22, or 25 cP at 400 C.

In certain embodiments, the compositions provided herein have dynamic viscosity of about 2 cP or greater at 1000 C. In certain embodiments, the compositions provided herein have dynamic viscosity of about 3 cP or greater at 1000 C. In certain embodiments, the compositions provided herein have dynamic viscosity from about 1 cP to about 10 cP, from about 1 cP to about 7 cP, or from about 2 cP to about 5 cP at 1000 C. In certain embodiments, the compositions have dynamic vis cosity ofabout 2, 3, 4 or 5 cP at 1000 C. The dynamic viscosity of the compositions disclosed herein can be measured accord ing to ASTM D 445.

In certain embodiments, compositions provided herein have a viscosity index about 90 or greater according to ASTM D 2270. In certain embodiments, compositions provided herein have a viscosity index about 100 or greater according to ASTM D 2270. In certain embodiments, the viscosity index is from about 90 to about 140 or about 100 to about 130 according to ASTM D 2270. In certain embodiments, the viscosity index is from about 110 to about 130 according to ASTM D 2270. In certain embodiments, the viscosity index is about 100, 110, 120, 125 or about 130 according to ASTM D 2270.

In certain embodiments, the compositions provided herein have density of about 0.700 to about 0.900 at 400 C. In certain embodiments, the compositions provided herein have density of about 0.700 to about 0.850 at 400 C. In certain embodi ments, the compositions provided herein have density of about 0.700, 0.750, 0.800, 0.850 or 0.900 at 400 C. In certain embodiments, the compositions provided herein have density of about 0.700 to about 0.800 at 1000 C. In certain embodi ments, the compositions provided herein have density of about 0.700, 0.750, or 0.800 at 1000 C.

In certain embodiments, provided herein are lubricant compositions. The lubricant compositions provided herein may further comprise a base oil and/ or a suitable lubricating oil additive.

In certain embodiments, the compositions provided herein have use as lubricity enhancers. In another embodiment, pro vided herein are lubricity enhancer compositions comprising compound II-A, a compound selected from squalane, squalene and dehydrosqualene, and a suitable lubricating oil additive. Any lubricating oil additive knoWn to a person of ordinary skill in the art may be used in the compositions disclosed herein. In some embodiments, the lubricating oil additive can be selected from the group consisting of antioxi dants, antiWear agents, detergents, rust inhibitors, demulsi? ers, friction modi?ers, multi-functional additives, pour point depressants, foam inhibitors, metal deactivators, dispersants, corrosion inhibitors, thermal stability improvers, dyes, mark ers, and combinations thereof.

In another embodiment, the lubricity enhancer composi tions provided herein further comprise a base oil of lubricat ing viscosity. Any base oil knoWn to a skilled artisan can be used as the oil of lubricating viscosity disclosed herein. Some base oils suitable for preparing the lubricant compositions have been described in Monier et al., “Chemistry and Tech nology 0f Lubricants, ” 2nd Edition, London, Springer, Chap ters 1 and 2 (1996); andA. Sequeria, Jr., “Lubricant Base Oil and Wax Processing,” NeW York, Marcel Decker, Chapter 6, (1994); and D. V. Brock, Lubrication Engineering, Vol. 43, pages 184-5, (1987), all of Which are incorporated herein by reference. In certain embodiments, the amount of the base oil in the composition is greater than about 1% based on the total Weight of the composition. In certain embodiments, the

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12 amount of the base oil in the composition is greater that about 2, 5, 15 or 20% based on the total Weight of the composition. In some embodiments, the amount of the base oil in the composition is from about 1-20% based on the total Weight of the composition. In certain embodiments, the amount of base oil in compositions provided herein is about 1%, 5%, 7%, 10%, 13%, 15%, or 20% based on total Weight of the com position.

In certain embodiments, the base oil is or comprises any natural or synthetic lubricating base oil fraction. Some non limiting examples of synthetic oils include oils, such as poly alphaole?ns or PAOs, prepared from the polymerization of at least one alpha-ole?n, such as ethylene, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases, such as the Fisher-Tropsch process.

In other embodiments, the base oil is or comprises a base stock or blend of base stocks. In further embodiments, the base stocks are manufactured using a variety of different processes including, but not limited to, distillation, solvent re?ning, hydrogen processing, oligomeriZation, esteri?ca tion, and rere?ning. In some embodiments, the base stocks comprise a rere?ned stock. In further embodiments, the rere?ned stock is substantially free from materials introduced through manufacturing, contamination, or previous use.

In some embodiments, the base oil comprises one or more of the base stocks in one or more of Groups I-V as speci?ed in the American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (i.e., API Base Oil Inter changeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils), Which is incorporated herein by refer ence. The API guideline de?nes a base stock as a lubricant component that may be manufactured using a variety of dif ferent processes. Groups I, II and III base stocks are mineral oils, each With speci?c ranges of the amount of saturates, sulfur content and viscosity index. Group IV base stocks are polyalphaole?ns (PAO). Group V base stocks include all other base stocks not included in Group I, II, III, or IV. The saturates levels, sulfur levels and viscosity indices for

Group I, II, III, IV and V base stocks are listed in Table 1 beloW.

TABLE 1

Viscosity Index (As determined by ASTM

Saturates (As Sulfur (As D 4294, ASTM D determined by ASTM determined by 4297 orASTM

Group D 2007) ASTM D 2270) D 3120)

I Less than 90% saturates.

Greater than or

equal to 0.03% sulfur.

Greater than or equal to 80 and less than 120.

II Greater than or equal Less than or Greater than or equal to 90% saturates. equal to 0.03% to 80 and less than

sulfur. 120. III Greater than or equal Less than or Greater than or equal

to 90% saturates. equal to 0.03% to 120. sulfur.

IV De?ned as

polyalphaole?ns (PAO)

V All other base stocks not included in Groups I, II, III or IV

In certain embodiments, the base oil is selected from the group consisting of natural oils of lubricating viscosity, syn thetic oils of lubricating viscosity and mixtures thereof. In some embodiments, the base oil includes base stocks obtained by isomeriZation of synthetic Wax and slack Wax, as Well as hydrocrackate base stocks produced by hydrocrack

US 7,691,792 B1 13

ing (rather than solvent extracting) the aromatic and polar components of the crude. In other embodiments, the base oil of lubricating viscosity includes natural oils, such as animal oils, vegetable oils, mineral oils (e.g., liquid petroleum oils and solvent treated or acid-treated mineral oils of the paraf ?nic, naphthenic or mixed paraf?nic-naphthenic types), oils derived from coal or shale, and combinations thereof. Some non-limiting examples of animal oils include bone oil, lano lin, ?sh oil, lard oil, dolphin oil, seal oil, shark oil, talloW oil, and Whale oil. Some non-limiting examples of vegetable oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sun?oWer oil, saf ?oWer oil, hemp oil, linseed oil, tung oil, oiticica oil, jojoba oil, and meadoW foam oil. Such oils may be partially or fully hydrogenated.

In some embodiments, the synthetic oils of lubricating viscosity include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymeriZed and inter-polymerized ole?ns, alkylbenZenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sul?des, as Well as their deriva tives, analogues and homologues thereof, and the like. In other embodiments, the synthetic oils include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof Wherein the terminal hydroxyl groups can be modi?ed by esteri?cation, etheri?cation, and the like. In further embodi ments, the synthetic oils include the esters of dicarboxylic acids With a variety of alcohols. In certain embodiments, the synthetic oils include esters made from C5 to C12 monocar boxylic acids and polyols and polyol ethers. In further embodiments, the synthetic oils include tri-alkyl phosphate ester oils, such as tri-n-butyl phosphate and tri-iso-butyl phosphate.

In some embodiments, the synthetic oils of lubricating viscosity include silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils and silicate oils). In other embodiments, the synthetic oils include liquid esters of phosphorus-containing acids, polymeric tetrahydro furans, polyalphaole?ns, and the like.

Base oil derived from the hydroisomeriZation of Wax may also be used, either alone or in combination With the aforesaid natural and/or synthetic base oil. Such Wax isomerate oil is produced by the hydroisomeriZation of natural or synthetic Waxes or mixtures thereof over a hydroisomeriZation catalyst.

In further embodiments, the base oil comprises a poly alpha-ole?n (PAO). In general, the poly-alpha-ole?ns may be derived from an alpha-ole?n having from about 2 to about 30, from about 4 to about 20, or from about 6 to about 16 carbon atoms. Non-limiting examples of suitable poly-alpha-ole?ns include those derived from octene, decene, mixtures thereof, and the like. These poly-alpha-ole?ns may have a viscosity from about 2 to about 15, from about 3 to about 12, or from about 4 to about 8 centistokes at 100° C. In some instances, the poly-alpha-ole?ns may be used together With other base oils such as mineral oils.

In further embodiments, the base oil comprises a polyalky lene glycol or a polyalkylene glycol derivative, Where the terminal hydroxyl groups of the polyalkylene glycol may be modi?ed by esteri?cation, etheri?cation, acetylation and the like. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyiso propylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of polyalkylene glycols (e.g., methyl ether of polyiso propylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), mono- and poly carboxylic esters of polyalkylene glycols, and combinations thereof. In some instances, the polyalkylene glycol or poly

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14 alkylene glycol derivative may be used together With other base oils such as poly-alpha-ole?ns and mineral oils.

In further embodiments, the base oil comprises any of the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, aZe laic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like) With a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, pro pylene glycol, and the like). Non-limiting examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di n-hexyl fumarate, dioctyl sebacate, diisooctyl aZelate, diiso decyl aZelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the like.

In further embodiments, the base oil comprises a hydro carbon prepared by the Fischer-Tropsch process. The Fis cher-Tropsch process prepares hydrocarbons from gases con taining hydrogen and carbon monoxide using a Fischer Tropsch catalyst. These hydrocarbons may require further processing in order to be useful as base oils. For example, the hydrocarbons may be deWaxed, hydroisomeriZed, and/or hydrocracked using processes knoWn to a person of ordinary skill in the art.

In further embodiments, the base oil comprises an unre ?ned oil, a re?ned oil, a rere?ned oil, or a mixture thereof. Unre?ned oils are those obtained directly from a natural or synthetic source Without further puri?cation treatment. Non limiting examples of unre?ned oils include shale oils obtained directly from retorting operations, petroleum oils obtained directly from primary distillation, and ester oils obtained directly from an esteri?cation process and used Without further treatment. Re?ned oils are similar to the unre ?ned oils except the former have been further treated by one or more puri?cation processes to improve one or more prop erties. Many such puri?cation processes are knoWn to those skilled in the art such as solvent extraction, secondary distil lation, acid or base extraction, ?ltration, percolation, and the like. Rere?ned oils are obtained by applying to re?ned oils processes similar to those used to obtain re?ned oils. Such rere?ned oils are also knoWn as reclaimed or reprocessed oils and often are additionally treated by processes directed to removal of spent additives and oil breakdoWn products.

In certain embodiments, the compositions provided herein have use as pour point depressant additives. In another embodiment, provided herein are pour point depressant addi tive compositions comprising compound II-A, a compound selected from squalane, squalene and dehydrosqualene, and a compatible solvent.

In certain embodiments, the compositions provided herein are used in combination With one or more other additives

knoWn in the art, for example the folloWing: detergents, par ticulate emission reducers, storage stabiliZers, antioxidants, corrosion inhibitors, dehaZers, demulsi?ers, antifoaming agents, cetane improvers, cosolvents, package compatibiliZ ers, and lubricity additives.

In certain embodiments, the pour point depressant additive composition provided herein further comprises an oil or a solvent miscible With oil. Examples of solvent are organic solvents including hydrocarbon solvents, for example petro leum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons; alcohols and/or esters; and par af?nic hydrocarbons such as hexane and pentane and isopar af?ns. The solvent is selected based on its compatibility With the additive and With the oil. Examples of oils for use herein include, crude oil or fuel oil. In certain embodiments, the oil

US 7,691,792 B1 15

is a lubricating oil, Which may be an animal, vegetable or mineral oil, such as petroleum oil fractions ranging from naphthas or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, ?sh oils, oxidized mineral oil, orbiodiesels. The pour point depressant compositions provided herein are useful in lubricating oils as How improvers, pour point depressants or deWaxing aids.

In certain embodiments, the compositions provided herein have use as fuel additives in fuels used to, for example, poWer internal combustion engines such as reciprocating engines (e.g., gasoline engines and diesel engines), Wankel engines, jet engines, some rocket engines, missile engines, and gas turbine engines. The compositions provided herein can be used in combination With other fuel additives knoWn in the art. Types of fuel additives include, but are not limited to, antioxidants, thermal stability improvers, cetane improvers, stabiliZers, cold ?oW improvers, combustion improvers, anti foams, anti-haZe additives, corrosion inhibitors, lubricity improvers, icing inhibitors, injector cleanliness additives, smoke suppressants, drag reducing additives, metal deactiva tors, dispersants, detergents, demulsi?ers, dyes, markers, static dissipaters, biocides, and combinations thereof.

Methods of Preparation The farnesene dimers and/or farnesane dimers for use in

compositions provided herein can be prepared dimeriZation of [3-farnesene as described in Example 1. In some embodi ments. [3-farnesene is derived from an isoprenoid starting material. In certain embodiments, the isoprenoid starting material is made by host cells by converting a carbon source into the isoprenoid starting material. Exemplary methods for making [3-famesene are described in Us. Pat. No. 7,399,323 Which is incorporated by reference in its entirety.

Heating neat farnesene to temperatures above 1200 C. ini tiates a Diels Alder dimeriZation process resulting in com pounds I-A, I-B, I-C and I-D. Reaction of the vinyl group of the diene With a second molecule of farnesene produces com pounds I-A or I-B depending on the orientation of the dieno phile. Reaction of the exo-methylene of famesene With the diene of a second molecule results in the formation of com pounds I-C or I-D, again depending on the orientation of the dienophile. In certain embodiments, compounds I-C and I-D come out just before compounds I-A and I-B With the ratio of peaks in order ofelution being 1.00: 1 .46: 5.67: 5.02. This may vary a little bit from run to run as measured by GC/ MS. GC/FID integration is slightly different in terms of ratios than the GC/MS. The relative ratios are the same but With slightly different magnitudes. In certain embodiments, the ratios are: 1.00:1.24:4.51:3.93.

In certain embodiments, the methods provided herein yield famesene dimers of formula I-A:I-B:I-C:I-D in a ratio of about 4:4: 1: 1 . In certain embodiments, the methods provided herein yield farnesane dimers of formula II-A:II-B:II-C:II-D in a ratio ofabout 4:4:1:1.

In certain embodiments, the reaction yields are quantitative except for physical losses if the crude product is ?ltered. In certain embodiments, the reaction is run from 150-2400 C. In certain embodiments, the temperature for the reaction is between 180-2000 C.

In certain embodiments, the hydrogenated dimers of for mula II-A, II-B, II-C and II-D canbe prepared by reducing the dimers of formula I-A, I-B, I-C and I-D in the presence of hydrogen With a catalyst such as Pd, Pd/ C, Pt, PtO2, Ru(PPh3) 2Cl2, Raney nickel, or combinations thereof. In one embodi ment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd/ C or 10% Pd/C. Alternatively, any reducing agent that can reduce a C:C bond to a CiC bond can also be used. For example, hydraZine in the presence of a catalyst,

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16 such as 5-ethyl-3 -methyllumi?avinium perchlorate, under 02 atmosphere can be used to give the corresponding hydroge nated products. The reduction reaction With hydraZine is dis closed in Imada et al., J. Am. Chem. Soc., 127, 14544-14545 (2005), Which is incorporated herein by reference.

In certain embodiments, dehydrosqualene can be prepared from famesene using a suitable catalyst. Exemplary catalysts include Palladium (II) acetylacetonate and triphenylphos phine, combination of [Palladium (II) nitrate, sodium (2-methoxyphenoxide) or sodium phenoxide and triph enylphosphine] (see e.g., BCS Japan, v.51(4), p. 1156-62 (1978) and Us. Pat. No. 3,859,374) as Well as the combina tion of [bis (cyclooctadiene)nickel and tributylphosphine] (see U.S. Pat. No. 3,794,692). In certain embodiments, poly merbound triphenylphosphine canbe used in place of soluble triphenylphosphine.

Squalane can be prepared by methods knoWn in the art. In one embodiment, squalane can be prepared by reducing dehy drosqualene in the presence of hydrogen With a catalyst such as Pd, Pd/C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or com binations thereof. The compositions disclosed herein can be prepared by any

method knoWn to a person of ordinary skill in the art for making lubricating oils. In some embodiments, the famesene dimers or farnesene dimers are blended or mixed With squalane, squalene or dehydrosqualene to obtain a lubricating oil composition. In certain embodiments, the lubricating oil compositions are further blended or mixed With other com ponents, such as one or more lubricating oil additives. Exem plary lubricating oil additives are described beloW. Any mix ing or dispersing equipment knoWn to a person of ordinary skill in the art may be used for blending, mixing or solubiliz ing the ingredients. The folloWing additive components are examples of some

of the components that can be added to compositions pro vided herein. These examples of additives are provided to illustrate the compositions, but they are not intended to limit them.

Additives Optionally, the composition may further comprise at least

one additive or a modi?er (hereinafter designated as “addi tive”) that can impart or improve any desirable property of the composition. In certain embodiments, the additive is a lubri cating oil additive. Any lubricating oil additive knoWn to a person of ordinary skill in the art may be used in the compo sitions disclosed herein. Some suitable additives have been described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” NeW York, Marcel Dekker (2003), both of Which are incorporated herein by reference. In some embodi ments, the additive can be selected from the group consisting of antioxidants, antiWear agents, detergents, rust inhibitors, demulsi?ers, friction modi?ers, multi-functional additives, pour point depressants, foam inhibitors, metal deactivators, dispersants, corrosion inhibitors, thermal stability improvers, dyes, markers, and combinations thereof.

In general, the concentration of each of the additives in the composition, When used, may range from about 0.001 Wt. % to about 20 Wt. %, from about 0.01 Wt. % to about 10 Wt. %, from about 0.1 Wt. % to about 5 Wt. % or from about 0.1 Wt. % to about 2.5 Wt. % based on the total Weight of the com position. Further, the total amount of the additives in the composition may range from about 0.001 Wt. % to about 30 Wt. %, from about 0.01 Wt. % to about 20 Wt. %, from about 0.1 Wt. % to about 10 Wt. %, or from about 0.1 Wt. % to about 5 Wt. %, based on the total Weight of the composition.

US 7,691,792 B1 17

Metal Detergents In some embodiments, a composition provided herein

comprises at least a neutral or overbased metal detergent as an additive, or additive components. In certain embodiments, the metal detergent prevents the formation of deposits on the surface of an engine. In certain embodiments, the detergent have additional functions, for example, as antioxidant. In certain aspects, compositions contain metal detergents com prising either overbased detergents or mixtures of neutral and overbased detergents. The term “overbased” is intended to de?ne additives Which contain a metal content in excess of that required by the stoichiometry of the particular metal and the particular organic acid used. The excess metal exists in the form of particles of inorganic base, eg a hydroxide or car bonate, surrounded by a sheath of metal salt. The sheath serves to maintain the particles in dispersion in a liquid ole aginous vehicle. The amount of excess metal is commonly expressed as the ratio of total equivalence of excess metal to equivalence of organic acid and is typically 0.1 to 30. Some non-limiting examples of suitable metal detergents

include sulfuriZed or unsulfuriZed alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sul furiZed or unsulfuriZed metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aro matic sulfonates, sulfuriZed or unsulfuriZed alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical and physical mix tures thereof. Other non-limiting examples of suitable metal detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li or the like. An exemplary metal detergent Which may be employed in the compositions includes overbased calcium phenate.

Generally, the amount of the metal detergent additive can be less than 10000 ppm, less than 1000 ppm, less than 100 ppm, or less than 10 ppm, based on the total Weight of the composition. In some embodiments, the amount of the metal detergent is from about 0.001 Wt. % to about 5 Wt. %, from about 0.05 Wt. % to about 3 Wt. %, or from about 0.1 Wt. % to about 1 Wt. %, based on the total Weight of the composition. Some suitable detergents have been described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applica tions,” NeW York, Marcel Dekker, Chapter 4, pages 113-136 (2003), both of Which are incorporated herein by reference.

SolubiliZing Agents SolubiliZing agents may be used in compositions provided

herein to increase solubility of various components in the composition. Suitable solubiliZing agents include, but are not limited to, oil-soluble esters and diesters, alkylated naphtha lenes, alkylated sulfones, naphthenic type base oils, aromatic type base oils, and alkylated benZenes. Other solubiliZing agents knoWn in the art are also contemplated herein. The esters and diesters that may be used as solubiliZing agents include, for example, adipate esters and polyol esters. Exem plary diesters include the adipates, aZelates, and sebacates of CS-Cl3 alkanols (or mixtures thereof), the phthalates of C4-Cl3 alkanols (or mixtures thereof). Mixtures of tWo or more different types of diesters (e.g., dialkyl adipates and dialkyl aZelates, etc.) may also be used. Examples of such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of adipic acid, aZelaic acid, and sebacic acid,

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1 8 and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid.

Anti Wear and/ or Extreme Pres sure Agents

In certain embodiments, compositions disclosed herein can additionally comprise anti Wear or extreme pressure agents. Wear occurs in all equipment that has moving parts in contact. Speci?cally, three conditions commonly lead to Wear in engines: (1) surface-to-surface contact; (2) surface contact With foreign matter; and (3) erosion due to corrosive materi als. Wear resulting from surface-to-surface contact is friction or adhesive Wear, from contact With foreign matter is abrasive Wear, and from contact With corrosive materials is corrosive Wear. Fatigue Wear is an additional type of Wear that is com mon in equipment Where surfaces are not only in contact but also experience repeated stresses for prolonged periods. Abrasive Wear can be prevented by installing an ef?cient ?ltration mechanism to remove the offending debris. Corro sive Wear can be addressed by using additives Which neutral iZe the reactive species that Would otherWise attack the metal surfaces. The control of adhesive Wear requires the use of additives called antiWear and extreme-pressure (EP) agents. Under optimal conditions of speed and load, the metal

surfaces of the equipment should be effectively separated by a lubricant ?lm. Increasing load, decreasing speed, or other Wise deviating from such optimal conditions promote metal to-metal contact. This contact typically causes a temperature increase in the contact Zone due to frictional heat, Which in turn leads to the loss of lubricant viscosity and hence its ?lm-forming ability. In certain embodiments, antiWear addi tive and EP agents offer protection by a similarmechanism. In certain embodiments, EP additives require higher activation temperatures and load than antiWear additives.

Without being bound to any particular theory, it is believed that antiWear and/ or EP additives function by thermal decom position and by forming products that react With the metal surface to form a solid protective layer. This solid metal ?lm ?lls the surface asperities and facilitates effective ?lm forma tion, thereby reducing friction and preventing Welding and surface Wear.

Most antiWear and extreme pressure agents contain sulfur, chlorine, phosphorus, boron, or combinations thereof. The classes of compounds that inhibit adhesive Wear include, for example, alkyl and aryl disul?des and polysul?des; dithio carbamates; chlorinated hydrocarbons; and phosphorus com pounds such as alkyl phosphites, phosphates, dithiophos phates, and alkenylphosphonates.

Exemplary antiWear agents that can be included in compo sitions provided herein include metal (e.g., Pb, Sb, and the like) salts of dithiophosphate, metal (e.g., Pb, Sb, and the like) salts of dithiocarbamate, metal (e.g., Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thio phosphoric acids and combinations thereof. The amount of the anti-Wear agent may vary from about 0.01 Wt. % to about 5 Wt. %, from about 0.05 Wt. % to about 3 Wt. %, or from about 0.1 Wt. % to about 1 Wt. %, based on the total Weight of the composition. Some suitable anti-Wear agents have been described in Leslie R. Rudnick, “LubricantAdditives: Chem istry andApplications,” NeWYork, Marcel Dekker, Chapter 8, pages 223-258 (2003), Which is incorporated herein by ref erence.

In one embodiment, the sulfated ash content of the total composition is less than Wt. %, less than 4 Wt. %, less than 3 Wt. %, less than 2 Wt. %, or less than 1 Wt. %, as measured according to ASTM D874.

US 7,691,792 B1 19

In one embodiment, the EP agents for use in compositions provided herein include alkyl and aryl disul?des and polysul ?des, dithiocarbamates, chlorinated hydrocarbons, dialkyl hydrogen phosphites, and salts of alkyl phosphoric acids. Methods of making these EP agents are knoWn in the art. For example, polysul?des are synthesized from ole?ns either by reacting With sulfur or sulfur halides, folloWed by dehydro halo genation. Dialkyldithiocarbamates are prepared either by neutraliZing dithiocarbamic acid (Which can be prepared by reacting a dialkylamine and carbon disul?de at loW tempera ture) With bases, such as antimony oxide, or by its addition to activated ole?ns, such as alkyl acrylates.

In certain embodiments, compositions provided herein comprise one or more EP agents. In one embodiment, use of more that one EP agent leads to synergism. For example, synergism may be observed betWeen sulfur and chlorine containing EP agents. An exemplary composition provided herein includes one or more EP agents selected from: Zinc dialkyldithiophosphate (primary alkyl type & secondary alkyl type), sulfuriZed oils, diphenyl sul?de, methyl trichlo rostearate, chlorinated naphthalene, ?uoroalkylpolysiloxane, and lead naphthenate.

Rust Inhibitors (Anti Rust Agents) Protection against rust is an important consideration in

formulating lubricants. Without protection, rust ultimately causes a loss of metal, thereby loWering the integrity of the equipment, and resulting in engine malfunction. In addition, corrosion exposes fresh metal that can Wear at an accelerated rate, perpetuated by the metal ions that might be released into the ?uid and act as oxidation promoters.

The composition disclosed herein can optionally comprise a rust inhibitor that can inhibit the corrosion of metal surfaces. Any rust inhibitor knoWn by a person of ordinary skill in the art may be used in the composition. The rust inhibitors attach themselves to metal surfaces to form an impenetrable protec tive ?lm, Which can be physically or chemically adsorbed to the surface. Speci?cally, ?lm formation occurs When the additives interact With the metal surface via their polar ends and associate With the lubricant via their nonpolar ends. Suit able rust inhibitors may include, for example, various non ionic polyoxyethylene surface active agents such as polyoxy ethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, poly oxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate. Suitable rust inhibitors may further include other compounds such as, for example, mono carboxylic acids (e.g., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid and the like), oil-soluble poly carboxylic acids (e. g., those produced from tall oil fatty acids, oleic acid, linoleic acid and the like), alkenylsuccinic acids in Which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, and the like); long-chain alpha, omega-dicarboxylic acids having a molecular Weight in the range of 600 to 3000 daltons and combinations thereof. Fur ther examples of rust agents include metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial car boxylic acid ester of polyhydric alcohol, and phosphoric ester.

Demulsi?ers The composition disclosed herein can optionally comprise

a demulsi?er that can promote oil-Water separation in com positions that are exposed to Water or steam. Any demulsi?er knoWn by a person of ordinary skill in the art may be used in

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20 the composition. Non-limiting examples of suitable demul si?ers include anionic surfactants (e. g., alkyl-naphthalene sulfonates, alkyl benZene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and combinations thereof. In certain embodiments, the demulsi ?ers for use herein include block copolymers of propylene oxide or ethylene oxide and initiators, such as, for example, glycerol, phenol, formaldehyde resins, soloxanes, polyamines, and polyols. In certain embodiments, the poly mers contain about 20 to about 50% ethylene oxide. These materials concentrate at the Water-oil interface and create loW viscosity Zones, thereby promoting droplet coalescence and gravity-driven phase separation. LoW molecular Weight mate rials, such as, for example, alkali metal or alkaline earth metal salts of dialkylnaphthalene sulfonic acids, are also useful in certain applications. The amount of the demulsi?er may vary from about 0.01 Wt. % to about 10 Wt. %, from about 0.05 Wt. % to about 5 Wt. %, or from about 0.1 Wt. % to about 3 Wt. %, based on the total Weight of the composition. Some suitable demulsi?ers have been described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), Which is incor porated herein by reference.

Friction Modi?ers The composition disclosed herein can optionally comprise

a friction modi?er that can loWer the friction betWeen moving parts. Any friction modi?er knoWn by a person of ordinary skill in the art may be used in the composition. They are typically long-chain molecules With a polar end group and a nonpolar linear hydrocarbon chain. The polar end groups either physically adsorb onto the metal surface or chemically react With it, While the hydrocarbon chain extends into the lubricant. The chains associated With one another and the lubricant to form a strong lubricant ?lm.

Non-limiting examples of suitable friction modi?ers include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof.

In one embodiment, the friction modi?er is a saturated fatty acid containing a 13 to 18 carbon chains. The amount of the friction modi?er may vary from about 0.01 Wt. % to about 10 Wt. %, from about 0.05 Wt. % to about 5 Wt. %, or from about 0.1 Wt. % to about 3 Wt. %, based on the total Weight of the composition. Some suitable friction modi?ers have been described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 183-187 (1996); and Leslie R. Rudnick, “Lubricant Addi tives: Chemistry and Applications,” NeW York, Marcel Dek ker, Chapters 6 and 7, pages 171-222 (2003), both of Which are incorporated herein by reference.

Seal SWell Agents Seal sWell agents may be included in the ?nished compo

sitions of the disclosed embodiments particularly When com positions provided herein are used as poWer transmission ?uids. Suitable seal sWell agents may be selected from oil soluble diesters, oil-soluble sulfones, silicon containing organic compounds, and mixtures thereof. Generally speak ing the most suitable diesters include the adipates, aZelates, and sebacates of CS-Cl3 alkanols (or mixtures thereof), and

US 7,691,792 B1 21

the phthalates of C4-Cl3 alkanols (or mixtures thereof). Mix tures of tWo or more different types of diesters (e.g., dialkyl adipates and dialkyl aZelates, etc.) may also be used. Examples of such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of adipic acid, aZelaic acid, and sebacic acid, and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid. Other esters Which may give generally equiva lent performance are polyol esters.

In one embodiment, the seal sWell agents are the oil soluble dialkyl esters of (i) adipic acid, (ii) sebacic acid, or (iii) phthalic acid.

Pour Point Depressants The composition disclosed herein can optionally comprise

a pour point depressant that can loWer the pour point of the composition. Any pour point depressant knoWn by a person of ordinary skill in the art may be used in the composition. In certain embodiments, pour point depressants possess one or more structural features selected from: (1) polymeric struc ture; (2) Waxy and non-Waxy components; (3) comb structure comprising a short backbone With long pendant groups; and (4) broad molecular Weight distribution. Non-limiting examples of suitable pour point depressants include poly methacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, alkyl fumarate polymers, di(tetra-para?in phenol) phthalate, condensates of tetra-paraf?n phenol, condensates of a chlorinated paraf?n With naphthalene, alkylated naph thalenes, styrene esters, oligomeriZed alkyl phenols, phthalic acid esters, ethylene-vinyl acetate copolymers and combina tions thereof. In one embodiment, the pourpoint depressant is selected from tetra (long-chain) alkyl silicates, phenyl tristearyloxysilane, and pentaerythritol tetrastearate. In some embodiments, the pour point depressant comprises an ethyl ene-vinyl acetate copolymer, a condensate of chlorinated par a?in and phenol, polyalkyl styrene or the like. The amount of the pour point depressant may vary from about 0.01 Wt. % to about 10 Wt. %, from about 0.05 Wt. % to about 5 Wt. %, or from about 0.1 Wt. % to about 3 Wt. %, based on the total Weight of the composition. Some suitable pour point depres sants have been described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 187-189 (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” NeW York, Marcel Dekker, Chapter 11, pages 329-354 (2003), both of Which are incorporated herein by reference. Foam Inhibitors The composition disclosed herein can optionally comprise

a foam inhibitor or an anti-foam that can break up foams in oils. Any foam inhibitor or anti-foam knoWn by a person of ordinary skill in the art may be used in the composition. Non-limiting examples of suitable anti-foams include sili cone oils or polydimethylsiloxanes, ?uorosilicones, alkoxy lated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines and combinations thereof. In some embodiments, the anti-foam comprises glyc erol monostearate, polyglycol palmitate, a trialkyl monothio phosphate, an ester of sulfonated ricinoleic acid, benZoylac etone, methyl salicylate, glycerol monooleate, or glycerol dioleate. The amount of the anti-foam may vary from about 0.01 Wt. % to about 5 Wt. %, from about 0.05 Wt. % to about 3 Wt. %, or from about 0.1 Wt. % to about 1 Wt. %, based on the total Weight of the composition. Some suitable anti-foams have been described in Mortier et al., “Chemistry and Tech nology of Lubricants, ” 2nd Edition, London, Springer, Chap ter 6, pages 190-193 (1996), Which is incorporated herein by reference.

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22 Metal Deactivators In some embodiments, the composition comprises at least

a metal deactivator. Some non-limiting examples of suitable metal deactivators include disalicylidene propylenediamine, triaZole derivatives, thiadiaZole derivatives, and mercapto benZimidaZoles.

Dispersants The composition disclosed herein can optionally comprise

a dispersant that can prevent sludge, vami sh, and other depos its by keeping particles suspended in a colloidal state. In certain embodiments, dispersants perform these functions via one or more means selected from: (1) solubiliZing polar con taminants in their micelles; (2) stabiliZing colloidal disper sions in order to prevent aggregation of their particles and their separation out of oil; (3) suspending such products, if they form, in the bulk lubricant; (4) modifying soot to mini miZe its aggregation and oil thickening; and (5) loWering surface/interfacial energy of undesirable materials to decrease their tendency to adhere to surfaces. The undesirable materials are typically formed as a result of oxidative degra dation of the lubricant, the reaction of chemically reactive species such as carboxylic acids With the metal surfaces in the engine, or the decomposition of thermally unstable lubricant additives such as, for example, extreme pressure agents.

In certain aspects, a dispersant molecule comprises three distinct structural features: (1) a hydrocarbyl group; (2) a polar group; and (3) a connecting group or a link. In certain embodiments, the hydrocarbyl group is polymeric in nature, and has a molecular Weight of at or above about 2000 Daltons, in one embodiment, at or above about 3000 Daltons, in another embodiment, at or above about 5000 Daltons, and in yet another embodiment, at or above about 8000 Daltons. A variety of ole?ns, such as polyisobutylene, polypropylene, polyalphaole?ns, and mixtures thereof, can be used to make suitable polymeric dispersants. In certain embodiments, the polymeric dispersant is a polyisobutylene-derived dispersant. Typically the number average molecular Weight of polyisobu tylene in those dispersants ranges betWeen about 500 and about 3000 Daltons, or, in some embodiments, betWeen about 800 to about 2000 Daltons, or in further embodiments, betWeen about 1000 to about 2000 Daltons. In certain embodiments, the polar group in the dispersant is nitrogen- or oxygen-derived. Nitrogen-based dispersants are typically derived from amines. The amines from Which the nitrogen based dispersants are derived are often polyalkylenep olyamines, such as, for example, diethylenetriamine and tri ethylenetetramine. Amine-derived dispersants are also called nitrogen- or amine-dispersants, While those derived from alcohol are also called oxygen or ester dispersants. Oxygen based dispersants are typically neutral While the amine-based dispersants are typically basic.

Non-limiting examples of suitable dispersants include alk enyl succinimides, alkenyl succinimides modi?ed With other organic compounds, alkenyl succinimides modi?ed by post treatment With ethylene carbonate or boric acid, succina mides, succinate esters, succinate ester-amides, pentaeryth ritols, phenate-salicylates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, disper sions of alkaline-earth metal borates, polyamide ashless dis persants, benZylamines, Mannich type dispersants, phospho rus-containing dispersants, and combinations thereof. The amount of the dispersant may vary from about 0.01 Wt. % to about 10 Wt. %, from about 0.05 Wt. % to about 7 Wt. %, or from about 0.1 Wt. % to about 4 Wt. %, based on the total Weight of the composition. Some suitable dispersants have been described in Monier et al., “Chemistry and Technology

US 7,691,792 B1 23

0f Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 86-90 (1996); and Leslie R. Rudnick, “LubricantAddi tives: Chemistry and Applications,” NeW York, Marcel Dek ker, Chapter 5, pages 137-170 (2003), both of Which are incorporated herein by reference.

Anti-Oxidants Optionally, the composition disclosed herein can further

comprise an additional antioxidant that can reduce or prevent the oxidation of the base oil. Any antioxidant knoWn by a person of ordinary skill in the art may be used in the compo sition. Examples of anti oxidants useful in compositions pro vided herein include, but are not limited to, phenol type (phenolic) oxidation inhibitors, such as 4,4' methylene bis (2,6 di tert butylphenol), 4,4' bis(2,6 di tert-butylphenol), 4,4' bis (2 methyl 6 tert butylphenol), 2,2' methylene bis(4-methyl 6 tert butylphenol), 4,4' butylidene bis (3 methyl 6 tert butylphenol), 4,4' isopropylidene bis(2,6 di tert butylphenol), 2,2' methylene bis(4-methyl 6 nonylphenol), 2,2' isobutyl idene bis(4,6 dimethylphenol), 2,2' 5 methylene bis(4 methyl 6 cyclohexylphenol), 2,6 di tert butyl 4-methylphenol, 2,6 di tert butyl 4 ethylphenol, 2,4 dimethyl 6 tert butyl-phenol, 2,6 di tert 1 dimethylamino p cresol, 2,6 di tert 4 (N,N'-dimethy laminomethylphenol), 4,4' thiobis (2 methyl 6 tert butylphe nol), 2,2'-thiobis (4 methyl 6 tert butylphenol), bis (3 methyl 4 hydroxy 5 tert-10 butylbenZyl) sul?de, and bis(3,5 di tert butyl 4 hydroxybenZyl). Diphenylamine type oxidation inhibitors include, but are not limited to, alkylated dipheny lamine, phenyl alpha naphthylamine, and alkylated alpha naphthylamine, sulfur-based antioxidants (e.g., dilauryl-3,3' thiodipropionate, sulfuriZed phenolic antioxidants and the like), phosphorous-based antioxidants (e.g., phosphites and the like), Zinc dithiophosphate, oil-soluble copper com pounds and combinations thereof. Other types of oxidation inhibitors include metal dithiocarbamate (e. g., Zinc dithiocar bamate), and 15 methylenebis(dibutyldithiocarbamate). The amount of the antioxidant may vary from about 0.01 Wt. % to about 10 Wt. %, from about 0.05 Wt % to about 5 Wt. %, or from about 0.1 Wt. % to about 3 Wt. %, based on the total Weight of the composition. Some suitable antioxidants have been described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” NeW York, Marcel Dekker, Chapter 1,pages 1-28 (2003), Which is incorporated herein by reference.

Multifunctional Additives Various additives mentioned or not mentioned herein can

provide a multiplicity of effects to the lubricant oil composi tion provided herein. Thus, for example, a single additive may act as a dispersant as Well as an oxidative inhibitor. Multi functional additives are Well knoWn in the art. Other suitable multi-functional additives may include, for example, sulfur iZed oxymolybdenum dithiocarbamate, sulfuriZed oxymo lybdenum organo phosphoro dithioate, oxymolybdenum monoglyceride, amine-molybdenum complex compound, and sulfur-containing molybdenum complex compounds.

Viscosity Index Improvers In certain embodiments, the composition comprises at

least a viscosity index improver. Some non-limiting examples of suitable viscosity index improvers include polymethacry late type polymers, ethylene-propylene copolymers, styrene isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improv ers.

Conductivity Enhancers In certain embodiments, the composition comprises at

least a conductivity enhancer. Some non-limiting examples of suitable conductivity enhancers include hydrogenated leci thin and related compounds; magnesium palmitate or alumi

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24 num palmitate or stearate; dihexyl esters of phosphoric acid neutraliZed With tetramethylnonylamines or C11-Cl4-alky lamines; monosodium phosphate derivatives of mono- and diglycerides composed of glyceride derivatives formed by reacting mono- and diglycerides that are derived from edible sources With phosphorus pentoxide (tetraphosphorus decox ide) folloWed by neutralization With sodium carbonate; phos phate derivatives of mono- and diglycerides produced as described above and reacted With ethanolamine and neutral iZed With fatty acid, and sodium dodecyl sulfonate.

Load-Bearing Additives In certain embodiments, the composition comprises one or

more load-bearing additives to reduce friction during metal Work processing. Exemplary load-hearing additives include, but are not limited to fatty alcohols, dicarboxylic acids or fatty acids and esters thereof, for instance fatty acid esters, butyl stearate, butyl palmitate, tridecyl aZelate and/ or dioctyl seba cate.

Uses of the Compositions The compositions provided herein are used in a Wide vari

ety of industrial applications associated With the automotive, tractor, airline, and railroad industries for use in engine oils, transmission ?uids, hydraulic ?uids, gear oils, energy/ shock absorbers poWer steering; metal-Working industry for use in metal sheets rolling or cutting machines and Water coolants; process oils for use in rubber and plastic processing; marine oils for use in propel engines; quench ?uids; greases; crank case lubricants; vehicle axle applications; and rotating machinery such as stationary engines, pumps, gas turbines, compressors, Wind turbines, and the like. Stationary engines include fuel and gas poWered engines that are not associated With the automotive, tractor, airline, and railroad industries. Exemplary automotive applications include, but are not lim ited to use in engine oils, for example, internal combustion engines, natural gas engines, turbine engines, automatic and manual transmissions and marine diesel engines. In certain embodiments, compositions provided herein have use as industrial oils, such as in hydraulic oils, ?re-resistant oils, industrial gear oils, railroad diesel and natural gas. In addi tion, the compositions based on embodiments described herein may be used in planetary hub reduction axles, mechanical steering and transfer gearboxes in utility vehicles such as trucks, synchromesh gear boxes, as Well as poWer take-off gears, limited slip axles, and planetary hub reduction gear boxes.

In one embodiment, compositions provided herein are use ful as engine lubricants. In one embodiment, provided herein is a method of lubricating an engine comprising operating the engine in contact With a composition provided herein.

In certain embodiments, provided herein is a method of lubricating a machine by operating the machine in contact With a composition provided herein. The compositions can be used for lubricating any machine that needs lubrication. Exemplary machines include, but are not limited to engines, pumps, gas turbines, compressors, Wind turbines, and the like. In certain embodiments, the engine is a fuel and/or gas poWered engine associated With the automotive, tractor, air line, and railroad industries. In certain embodiments, the engine is a stationary engine, including a fuel and/or gas poWered engine that is not associated With the automotive, tractor, airline, and railroad industries. In certain embodi ments, provided herein is a machine comprising a composi tion provided herein.

In one embodiment, a composition provided herein is an automatic transmission ?uid (ATF). An exemplary ATF com position additionally contains a solubiliZing agent, from about 0.5 to about 1.5 Wt. % viscosity index improver, from

US 7,691,792 B1 25

about 1.5 to about 2.5 Wt % ashless dispersant, from about 0.05 to about 1 Wt. % friction modi?er, from about 0.01 to about 0.5 Wt. % corrosion inhibitor, from about 0.1 to about 0.4 Wt. % antiWear additive, from about 0.005 to about 5 Wt. % metal deactivator, from about 0.1 to about 15 Wt. % metal lic detergent, from about 0.25 to about 1 Wt. % seal sWell agent, from about 0.01 to about 0.5 Wt. % pour point depres sant and optionally a base oil component.

In one embodiment, the ?nished composition is a manual transmission oil. An exemplary manual transmission lubri cating oil formulation further contains a solubiliZing agent, a viscosity index improver, an ashless dispersant, at least one antioxidant, at least one inhibitor and optionally a base oil component.

In another embodiment of the disclosure, the ?nished com position is an axle lubricating oil. An exemplary axle lubri cating oil formulation contains a solubiliZing agent, a viscos ity index improver, a sulfur containing extreme pres sure agent, at least one phosphorus containing anti-Wear agent, at least one ashless dispersant, at least one inhibitor and option ally a base oil component.

In one embodiment, compositions provided herein are used as a crankcase lubricant and may include a solubiliZing agent, a viscosity index improver, a detergent, a dispersant, an anti Wear agent, a friction modi?er, an antioxidant, a corrosion inhibitor, a pour point depressant, an anti-foam agent and optionally a base oil component.

The compositions described herein may also be used in quench ?uid applications to provide a sloWer rate of cooling for hardening metals such as steel. Quench ?uid performance may be modi?ed by introducing one or more of the foregoing additives and/or compositions to improve Wettability, cooling rates, oil stability life, and to reduce deposit forming tenden cies of the quench ?uids.

While the compositions and methods have been described With respect to a limited number of embodiments, the speci?c features of one embodiment should not be attributed to other embodiments described herein. No single embodiment is rep resentative of all aspects of the compositions or methods. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of any compounds or steps not enumerated herein. Variations and modi?cations from the described embodiments exist.

All publications and patent applications mentioned in this speci?cation are herein incorporated by reference to the same extent as if each individual publication or patent application Was speci?cally and individually indicated to be incorporated by reference. Although the foregoing has been described in some detail by Way of illustration and example for purposes of clarity of understanding, it Will be readily apparent to those of ordinary skill in the art in light of the teachings herein that certain changes and modi?cations may be made thereto With out departing from the spirit or scope of the appended claims.

EXAMPLES

The practice of the present subject matter can employ, unless otherWise indicated, conventional techniques in the industry and the like, Which are Within the skill of the art. To the extent such techniques are not described fully herein, one can ?nd ample reference to them in the scienti?c literature.

In the folloWing examples, efforts have been made to ensure accuracy With respect to numbers used (for example, amounts, temperature, and so on), but variation and deviation can be accommodated, and in the event a clerical error in the

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26 numbers reported herein exists, one of ordinary skill in the arts can deduce the correct amount in vieW of the remaining disclosure herein. Unless indicated otherWise, temperature is reported in degrees Celsius. All reagents, unless otherWise indicated, Were obtained commercially. [3-famesene used herein is prepared as described in Us. Pat. No. 7,399,323 Which is incorporated by reference in its entirety. The folloW ing examples are intended for illustrative purposes only and do not limit in any Way the scope of the present invention.

Example 1

This example describes a method for making famesene dimers from [3-famesene.

To a 500 mL three-necked round-bottomed ?ask, previ ously rinsed With conc. NH4OH solution and dried, equipped With a magnetic stirrer, heating mantle, thermometer, re?ux condenser and nitrogen inlet Were added 204 g (1.00 mol) of [3-famesene (Bedoukian, 98%). The farnesene Was stirred and heated to 220° C. While monitoring the progress of the reac tion by GC/MS. After tWo hours the colorless reaction mix ture consisted almost entirely of tWo pairs of dimers, l-A:l-C in a ratio of 4:1 and l-B:l-D in a ratio of 4:1 With <2% of starting material remaining. The mixture Was alloWed to cool to approximately 50° C. and vacuum ?ltered through a 0.5 cm thick layer of Celite on a 60 mL medium porosity sintered glass funnel to afford 200 g (98.3%) of clear colorless oil. The compositions comprise compounds l-A, l-C, l-B, and l-D Which Was con?rmed by 1H and 13C NMR.

Farnesene dimers: 1H (400 MHZ, CDCl3) d (multiplicity, coupling constant{s}, integration*), 5.71 (dd, 1:56 and 10.8 HZ, 0.04H), 5.65 (dd, 1:56 and 10.8 HZ, 0.04H), 5.37 (m, 0.60H), 5.12 (m, 3.04H), 5.01 (dt, 1:1 .6 and 10.8 HZ, 0.10H), 4.89 (ddd, 1:16, 12.0 and 17.6 HZ, 0.06H), 4.74 (m, 1.00H), 2.09 (m, 9.28H), 1.98 (m, 5.30H), 1.68 (s, 4.24H), 1.60 (s, 7.97H) ppm. *Integration values are relative areas peak to peak and not absolute numbers of protons.

Farnesene dimers: 13C (100 MHZ, CDCl3) d 154.36, 154.26, 146.14, 145.44, 145.25, 139.55, 139.04, 137.46, 137.39, 136.94, 135.87, 135.38, 135.11, 135.07, 134.94, 134.82, 134.59, 131.225, 125.01, 124.97, 124.44, 124.34, 124.23, 124.06, 122.71, 120.47, 120.37, 120.17, 119.16, 115.71, 113.02, 112.11, 112.01, 107.24, 107.18, 40.39, 40.25, 40.17, 40.13, 40.00, 39.74, 38.72, 38.16, 38.04, 37.87, 37.61,34.89,34.63,34,55,3227,31.76,31.47,29.10,28.41, 28.03, 27.25, 26.77, 26.65, 26.43, 26.41, 26.34, 25.88, 25.82, 25.69, 22.73, 22.46, 22.41, 17.68, 16.05, 16.02, 15.93 ppm.

Example 2

This example describes method for making famesane dimers from famesene dimers. A mixture of famesene dimers (100 g, 0.245 mol) Was

placed in a 1 L glass lined Hastaloy Parr hydrogenation vessel containing 0.75 g of 5% Pd/C. Hexane (300 mL) Was added and the reactor assembled. The mixture Was placed under vacuum for one hour. The stirrer Was started (400 rpm) and the reactor Was pressuriZed to 600 psig With hydrogen. The mixture Was heated to 72° C. and the pressure alloWed to drop to 300 psig at Which time hydrogen Was added to bring the pressure back to 600 psig. This process Was repeated until hydrogen consumption had ceased. The reactor Was alloWed to cool to 30° C. and the contents Were ?ltered to remove the catalyst. Removal of the solvent under reduced pressure afforded 100 g (96.9%) of farnesane dimers consisting of 15 isomeric compounds of molecular Weight 420 (GC/MS).

US 7,691,792 B1 27

Celite on a 60 mL medium porosity sintered glass funnel to afford 200 g (98.3%) of clear colorless oil. The presence of compounds II-A, II-C, II-B, and II-D Were con?rmed by 1H NMR.

1H (400 MHZ, CDCl3) d (multiplicity, coupling constant{s}, integration*) 1.79-1.55 (m, 4.08H), 1.52 (m, 1:68 HZ, 4.94H), 1.59-1.00 (m, 53.95H), 1.05, 0.87, 0.86, 0.85, 0.85, 0.83, 0.83, 0.82, 0.81, 0.80, 0.79 (s, 36.01 total H). *Integration values are relative areas peak to peak and not absolute numbers of protons.

Farnesane 1,4-Dimer (90% pure): 1H (400 MHZ, CDCl3) d (multiplicity, coupling constant {s}, integration*) 5.42 (m, 1H), 5.12 (m, 4H), 4.75 (m, 2H), 2.10 (m, 15H), 1.98 (m, 8H), 1.682 (s, 3H), 1.680 (s, 3H), 1.60 (s, 12H) ppm.

Example 3

Preparation of Dehydrosqualene from Farnesene

Farnesene (331.94 g, 1.627 mmol) Was stirred in 1025 mL 2-propanol and triphenylphosphine (9.55 g, 36.4 mmol) Was added folloWed by Palladium (II) acetylacetonate (3.91 g, 13 .0 mmol). The mixture Was heated at 85° C. for 7 hours and then alloWed to cool to 25° C. After stirring 17 hours, most of the 2-propanol Was removed by rotary evaporation and the black residue Was suspended in one liter of 5% ethyl acetate in hexanes. The suspension Was ?ltered through a silica gel pad 3 inches in diameter><3 inches high and the silica gel Was Washed With 500 mL 5% ethyl acetate in hexanes. The com bined organic solutions Were concentrated by rotary evapo ration to give 328.3 g light yelloW oil.

Alternative catalysts for this reaction include the combina tion of [Palladium (II) nitrate, sodium (2-methoxyphenoxide) or sodium phenoxide and triphenylphosphine] (see e.g., BCS Japan, v.51(4), p. 1156-62 (1978) and Us. Pat. No. 3,859, 374) as Well as the combination of [bis(cyclooctadiene)nickel and tributylphosphine] (U .8. Pat. No. 3,794,692). In certain embodiments, polymer bound triphenylphosphine can be used in place of soluble triphenylphosphine. Other catalysts that Were tried but Which gave no useful conversion (<5%) include 5% Pd/C, 5% Pd/alumina, 5% Ru/ C, palladium acetate, copper (II) acetylacetonate, cobalt (II) acetylaceto nate, nickel (II) acetylacetonate, palladium (II) acetylaceto nate (With no phosphine ligand), palladium chloride triph enylphosphine and palladium (0) dibenZylideneacetone triphenylphosphine.

Example 4

Preparation of Squalane from Dehydrosqualene

Dehydrosqualene prepared above Was placed in a one liter Parr pressure reactor and 1.1 g of 5% Pd/C Was added. The vessel Was sealed and evacuated under house vacuum for

tWenty minutes (ca. 20 ton) and then pressurized With hydro gen gas up to 950 psi. The reaction is initially exothermic. After the initial exothermic stage of the reaction Was com

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28 plete the reaction temperature Was maintained at 40° C. by external heating and later at 60° C. Hydrogen gas Was added

as needed to maintain the reaction rate. After 47 hours the

reaction Was judged complete by GCMS analysis so the crude reaction product Was ?ltered through a silica gel pad 3 inches in diameter><3 inches high and the silica gel Was Washed With 550 mL 5% ethyl acetate in hexanes. After removal of the

solvent by rotary evaporation the crude squalane Weighed 332.6 g. The product Was distilled in 3 batches using a Kugel rohr bulb to bulb apparatus to give 282.4 g squalane (83.4% yield over both steps).

Example 5

This example provides lubricant properties for the fame sane dimers prepared according to Example 2 and squalane prepared according to Example 4.

TABLE 2

Thermal ASTM Farnasane Method Squalane Dimer

Viscosity at 40° C., cst D 445 19.23 35.44 Viscosity at 100° C., cst D 445 4.14 5.71 Kinematic Viscosity, cSt, D 445 6109.19 39410.14 —40° C. Viscosity index D 2270 118-132 100 Pour Point, ° C. D 97 <—60 C. —57 Flash Point, COC, ° C. D 92 232 234 Evaporative Loss, D 5800 13.2 9.1 NOACK, Wt. % Acid Number (mg D 974 0.056 1.25 KOH/g)

In certain embodiment, depending on the reaction condi tions for making the famesene/farnesane dimers (according to Example 1 and 2), some amounts of higher oligomers may be also present in the ?nal compositions. The famesane dimers tested in this example Were distilled to remove any

higher oligomers that may be present. In addition, thermal farnesene dimers have a viscosity at

40° C. of 17 cSt and a viscosity at 100° C. of 5.03 cSt. The viscosity index of the thermal farnesene dimers Was found to be 255.

Example 6

This example provides lubricant properties for various blends of farnesane dimers (II-A, II-B, II-C and II-D) and squalane. This example provides lubricant properties for the famesane dimers prepared according to Example 2 and squalane prepared according to Example 4. The famesane dimers tested in this example Were distilled to remove any higher oligomers that may be present.

US 7,691,792 B1

Example 7 TABLE 3

% % This example provides lubricant properties for various Fallwsane Squa' 5 blends of farnesene dimers (l-A, l-B, l-C and l-D) and dimers lane d40 dloo cP4O cSt4O cPlOO cStlOO VI _ _ _ _

squalane. This example prov1des lubricant properties for the 0 100 0.800 0.764 14.9 18.6 3.20 4.18 132 - -

20 80 0801 0763 172 216 3A8 454 127 famesene d1mers prepared according to Example 2 and 20 80 0.801 0.763 17.4 21.8 3.48 4.54 125 squalane prepared according to Example 4. The famesene 40 60 0.797 0.767 19.3 24.1 4.56 5.76 115 ~ ~ ~ ~ ~

80 20 0831 0763 25A 306 423 554 119 10 dimers tested in this example were distilled to remove any 100 0 0.825 0.792 30.1 36.5 3.60 5.71 103 higher ol1gomers that may be present.

dx is the density at temperature x. cPx is the dynamic (absolute) viscosity at temperature x (in centipoises). TABLE 7 cStx is the kinetic viscosity at temperature x (in centistokes).

15 In certain embodiment, a composition provided herein may 1541111686116 %

comprise blends famesane dimers (ll-A, ll-B, ll-C and ll-D) ‘11mm Squalane °St40 cstloo VI and squalene as described in Table 4: 20 80 180 459 185

50 50 17.2 4.58 200

TABLE 4 20 80 20 17.0 4.56 202

%

Farnesane % Since modi?cations Will be apparent to those of skill in the dimers Squal?ne art, it is intended that the claimed subject matter be limited

0 100 nlbth fth ddl'. 20 80 25 o y y e scope o e appen e c a1ms

20 80 40 60

128 28 What is claimed is: 1. A composition comprising compound ll-A, and a com

30 In certain embodiment, a composition provided herein may Pound Selected from Squalane, squalene, and (613,1 1111813)

comprise blends famesane dimers (ll-A, ll-B, ll-C and ll-D) 2,6,19,23-tetramethyl-l0,l5-dimethylenetetracosa-2,6,l1, and dehydrosqualene as described in Table 5: 18, ggpemaenea wherein Compound ILA is

TABLE 5 35 lI-A

% Farnesane % dimers dehydrosqualene

0 100 20 80 40 20 80 40 60 80 20 100 0

2. The composition of claim 1 further comprising com pound ll-B

- 3. The composition of claim 1 further comprising a com pound selected from:

Il-C

US 7,691,792 B1 31 32

-continued

4. The composition of claim 1 comprising compound ll-A and squalane.

5. The composition of claim 4 further comprising com pound ll-B.

6. The composition of claim 5 further comprising a com pound selected from l-A, l-B, l-C, l-D, ll-C and ll-D.

7. The composition of claim 1, Wherein compound ll-A is present in about 1% or greater based on total Weight of the composition.

8. The composition of claim 1, Wherein compound ll-A is present in about 20% or greater based on total Weight of the composition.

9. The composition of claim 1, Wherein compound ll-A is present in about 40% or greater based on total Weight of the composition.

10. The composition of claim 2, Wherein compound ll-B is present in about 1% or greater based on total Weight of the composition.

11. The composition of claim 2, Wherein compound ll-B is present in about 20% or greater based on total Weight of the composition.

12. The composition of claim 2, Wherein compound ll-B is present in about 40% or greater based on total Weight of the composition.

13. The composition of claim 1, Wherein squalane is present in about 1% or greater based on total Weight of the composition.

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14. The composition of claim 13, Wherein squalane is present in about 20% or greater based on total Weight of the composition.

15. The composition of claim 1, Wherein squalene is present in about 1% or greater based on total Weight of the composition.

16. The composition of claim 1, Wherein (6E,11E,18E)-2, 6,19,23-tetramethyl-10,15-dimethylenetetracosa-2,6,1 1,18, 22-pentaene is present in about 1% or greater based on total Weight of the composition.

17. The composition of claim 1 that is a lubricant compo sition.

18. The composition of claim 1 further comprising at least one additive selected from the group consisting of an antioxi dant, an antiWear agent, a detergent, a rust inhibitor, a demul si?er, a friction modi?er, a multi-functional additive, a Vis cosity index improver, a pour point depressant, a foam inhibitor, a metal deactivator, a dispersant, a corrosion inhibi tor, a lubricity improver, a solubiliZing agent, a seal-sWell agent and a combination thereof.

19. A method of lubricating a machine comprising the step of operating the machine in contact With the composition of claim 1.

20. A machine comprising the composition of claim 1, Wherein the composition is used to lubricate the machine.

* * * * *